Intermediate and dyestuff of the dibenzanthrone series



Patented Aug. 29, 1933 INTERMEDIATE AND DYESTUFF' DIBENZANTHRONE'SERIES Melvin A. Perkins, Carneys Point, J., assignor l to E. I. du Pont de Nemours & Company, Wilmington, Del., acorporation of Delaware No JDrawing. Appl cation February 11, 1930 Serial No. 427,654 Y 19 Claims. (01. 260-61) This invention relates to an organic chemical compound and a method of producing it. More particularly it relatesto a dyestuff intermediate of the benzanthrone series and dyestuffs pro- 5 duced therefrom.

An object'of the invention is to produce new and valuable chemical compounds. 1 Other obj ects are to produce'dyestufis intermediates of a novel type, to develop a new and improved process of producing benzanthrone derivatives, to develop a process of producing Bz-1-Bz-1-benzanthronyl compounds which avoids the use of an acid binder, and to produce dyestuffs of distinctive shades and superior properties. Other objects will appear hereinafter.

These objects are accomplished by the following. invention whereby a compound having the probable structural, formula g is produced. p r

The compound may be produced by heating BZ? l-halogen-benzanthrone with selenium powder in a high-boiling solvent, preferably one which is rich in hydrogen, with or without some additional, substance capable of reacting readily witha halogen, a halogen acid, or both. There is obtained as a resultof this process a benzanthronyl derivative containing chemically bound selenium. This L derivative crystallizes readily fromsuitable solvents in thick, pointed needles of a golden yellow sented as follows;

The hydrogen indicated in the above equation is very likely furnished by the solvent.

The invention will be readily understood from color. The probable final reaction may be rep'Ieconsideration of the following specific examples.

The proportions are given by weight. l

w Example I Q One hundred (100) parts of Bz-l-bromobenzan throne, 14 parts of fine selenium powder,- and 20: parts of powdered lime are stirred vigorously and heated eight hours at 220 C. in 500parts of high boiling kerosene or until the; solid reaction' product gives a strong green-blue coloration when dissolved in concentrated sulphuric acid .v Since Bz l-bromobenzanthrone givesa red coloration V in sulphuric acid, this color test gives indication of the extent of the reaction. After'the reaction 6 is complete, the mixture is cooled to50, C.- and filtered, washed thoroughly with hot water,,dried and delimed by hydrochloric acid, 1 J

- tfEwa'l nple II I To'a solution of 100 parts of Bz-l-bromobenzanthrone in 300 parts of trichloroben zene is added 200 parts of high-boiling" kerosene and 14 .parts of selenium, and the whole is heated at 210-220 ,C. until thereaction product gives a green-blue coloration when dissolved in' concentrated sulphuric acid. The solution is then cooled andthe reaction-product filtered off and dried.- The product is similar to that obtained in Example I, but free from lime or inorganic'salts;

Bz-l-chlorobenzanthrone (60 grams) prepared by chlorination of, benzanthrone in orthodi chlorobenzene ornitrobenzene by means of sul-, phur chloride or chlorine,gas,f is dissolved in tetrahydronaphthalene (300 grams); sodium acetate (20.5}grams) andrselenium (10.0 grams) are then added'and the mixture heatedto reflux temperature until a test sample gives aclea'r greenish-blue solution in concentrated sulphuric acid. The mixture is then allowed to cooland 110 thesolid is separated, washed and dried as usual.

. The product is identical with thatobtained in both bromine and selenium.

Examples I and'll.

The product obtained by the above processes is a granular brownish-yellow powder, very sparingly soluble in' cold organic solvents, but fairly soluble ,in hot. nitro'benzene or 'ortho-dichloro-- benzene, from which it crystallizes readily in.

thick,'pointed needles of a golden yellow color.

Theproduct dissolves in concentrated sulphuric acid with strong, clear, very greenish-blue colora-- tion. It is practically insoluble in alkaline sodi um hydro'sulphite; After. extraction by sodium sulphide solution, to remove excess selenium, and recrystallization from intro-benzene, the product shows'a melting. point of 336-337" C. and."

a selenium content of 14.97% by analysis. The theoretical percentage of selenium contained in Bz-l;Bz-1-benzanthronyl selenide is 14.74.

Example IV reflux for twohours or until a sample gives a bluish-green solution in concentrated sulphuric acid. The'reaction mixture is then cooled, filtered, and the filter cake is'washed withalcohol and finally with water and is then-dried. The

product is a brownish-orange powder, containing readily from hot nitroben'zene, giving thin curved needles of an orange color. 7 3 a The Bz-l-Bz-l-benzanthronyl-selenidemay be readily condensed to iormisoviolanthrone as Twill be obvious from the following example.

to 80 C. and'198 parts of flaked caustic potash" Example V v Twent -six (26 parts of sodium are dissolved in 172 partsfof 93 alcoholpthe solution warmed added; After this been stirred one-half hour, thetemperature is adjusted to 11o to 120? liquor;

co, 'E'fsition is kept nee. It is necessary to keep this position free if the 'Bz-hBz-l benzan- C. and lOQparts of the intermediate, BzQl-Bzd' be'nzanthronyl. selenide, V

which the temperature is raised to 135 to 140 C. and; maintained for one hour. The melt is slowly added, after drowned in water, oxidized by air, and the dyestuff ,isolated in the usual manner. Selenium may be re'coverd as such from the aerationmother- The process unsubstituted Bzl'-bromobenzanthrone. Substituents may be joined to the Bz-l-bromo benzanthrone molecule .so long as the 2 pothronyl selenide is to be condensed to iso'violanthrone. This will be clear from consideration ,of the formulas above submitted, whi'ch show :that the reaction involves only thepositions 3Z1,

Bzl' and is therefore generally nothindered by substituents in the other positions. I It should be understood that the invention is not limited to the useof a single Bz1-halogen-' "benzanthrone. vantageously treated. In such cases the result- Various mixtures may be adant Bz-l-Bz-l-benzanthronyl selenide may or may notbesymmetrical, or a mixtureof various iBz-l-Bz-l -benzanthronyl selenides may be pro- It recrystallizes' herein set out :is not limited to,

duped. The exact composition of the product will depend upon such factors as solubility, chem- 7 "ical activity and the like.

Of the halogen compounds, Bz-l-chlor'oben-V za'nthronev and Bz-l-bromobenzanthrone are preferred. Especially good results have been obtained with Bzl-bromobenzanthrone.

Other materials capable of reacting with halogen. or halogen acid may be used in place of lime,

for example, sodium acetate, sodium s'ulfite,-so-

diumbisulfite, sodiumcarbonate or sodium benmate. The corresponding ammonium salts or alkali metal salts'such as potassium may be used for the sodium salts listed. As a further modification ammonia gas may be passedover the boiling mixture to accomplish a similar result. Although any highboi'ling solvent maybe used (or alow-boiling solvent under pressure) it is preferable to use a solvent which is readily halogenated, or one which is rich in hydrogen. Examples of these are high boiling petroleum oils,

-hydrogenated naphthalenes' such as the di tetra-, hexa-, or deca-hydronaphthalene, kero sene, paraffin or trichlorobenzene when mixed with any of these.

If a benzanthrone is present the Bz-1-Bz-1'- benzanthronyl selenide fusion an increase in the yield of insoviola'nthrone is obtained. The yield becomes'greater with increases in the amount of the benzanthrone until the'ratio of one molecule ofbenzanthrone to each molecule of Bz-l- Bz-l'f benzanthronyl selenide is reached.

The new selenium derivative of the benzanthrone series is a'valuable intermediate for benzanthrone vat colors. Treatment of this intermediate, either alone or in conjunctionv with benzanthrone as indicated above, by means of alkaline condensing agents produces insoviolanthrone of high purity.

V Isoviolanthrone made from this new intermediate gives,directly, dyeings of good brightness and very reddish shade; and can be chlorinated with high yields of a product which yields strong, bright, and exceptionally reddish shades of violet. Isoviolanthrone prepared from Bz -l-Bz-l benzanthronyl-selenide apparently gives redder shades than that produced from dibenzanthronyl-sulfide. I 1

Asmany apparently widely different. embofdi merits of this invention may be made without departing ,fromthe spirit andscope thereof, it'is; to be understood that'I do not limit myself to'the specific embodiments thereof except as defined parts of Bz-l-bromobenzanthrone, 14 parts of fine selenium powder and 20 parts oflime together and. heatingsubstantiallyfi hours at about 220 C. in 500 parts or high boiling, kerosene or until the solid reaction product 'givesa strong greenblue coloration when dissolved. in concentrated sulfuric acid.)

LA method of producing Bz-l -Bzrl -benzanthronyl' selenide which comprises stirring. a mixture of. selenium and Bz'1-bromobenzan,-"

the pres an acid absorbing agent.

throne in the ratio of one atom of selenium with two molecules of Bz-l-bromobenzanthrone in high-boiling kerosene and heating at about 220 reaction, until a sample of the solid reaction product gives a green blue coloration when dissolved in concentrated sulphuric acid, ,thereafter cooling to about 50 C., filtering, washing with hot water,

drying and deliming. I

5. The product which is substantially identical with that obtainable. by condensing Bzl-Bz-rbenzanthronyl selenide in an alkali fusion.

X and Y may be alike or different and each stands for a benzanthronyl radical having a free 2-position. i

7. The product which is substantially identical with that obtainable by condensing Bz-l-Bz-lG- benzanthrone selenide in the presence-of alco 9. Textile material'dyed with the dyestulf produced by fusing the product of claim 4 in a causticalkali melt at about 110 C. to 140 C. 10. The process of preparing a benzanthrone derivative containing selenium, which comprises reacting with finely divided selenium upon a solution of a Bzl-halogen-benzanthrone having a free 2- position in an organic solvent.

11.-.The process of preparing a benzanthronederivative containing selenium, which comprises heating a solution of Bzl-halogen-benzanthrone,

. in an organic solvent which is rich in hydrogen,

with finely divided selenium in the possessing the nuclear structure of Bzl, Bzl dibenzanthronyl selenide and being adapted to yield a dyestufi of the isoviolanthronev series by stituents in the 2,2'-positions.

12. The; process of preparingabenzanthrone derivative containing selenium. which comprises refluxing a mixture of Bzl-halogen-benzanthrone, tetrahydronaphthalene, sodium acetate and. selenium, until a test sample givesa' clear greenish; blue solution concentrated sulfuric acid.

5 13. The process of preparing a benz'anthrone derivative containing selenium, which comprisesheating to about-210-#220 C. a'mixture'of Bzlhalogen-benzanthrone, high boiling kerosene,, lime, and selenium, until a test sample gives no further a red'color when dissolved in concen- V trated sulfuric acid. 6. The product of the formula X-Se-Y where 14. A compound of the benzanthrone series.

fusion with alcoholic caustic potash. I

' 15. Bzl, Bz1 -dibenzanthronyl selenide.

16. A Bzl, Bzl -diben'zanth'ronyl selenide which may be substituted by halogen but has no sub- Y 1'7. A derivative of the benz 'anthrone series containing selenium, being substantially. identi- Y (ml with the compound obtainable by reacting 10 with selenium a Bzl-halogenated benzanthrone having a free 2-position.

18. .The process of preparing a dyestuff of the isoviolanthrone series which comprises reacting a Bzl-halogen-benzanthrone havinga free2-position with selenium to give a Bzl-selenium-ben zanthronecompound, and subjecting the latter to caustic fusion to form the corresponding isoviolanthrone' compound.

19. The process which comprises reacting 321- V 1 halogen-benzanthrone with selenium togive Bzl, presence of.

Bzl-benzanthronyl selenide, and subjecting the latter to caustic fusion to formisoviolanthrone.

. MELVIN A. PERKINS. 

